Detergent composition

ABSTRACT

A liquid hard surface detergent composition comprising a liquid mixed alkoxylate fatty alcohol non-ionic surfactant comprising a greater number of the lower higher alkoxylate group than the higher alkoxylate group in the molecule and a builder. The compositions provide good shine/anti-spotting characteristics on hard surfaces and are especially suitable for use as automatic dishwashing compositions.

This is an application filed under 35 USC 371 of PCT/GB2010/051670.

TECHNICAL FIELD

The present invention relates to hard surface detergent compositionssuch as dishwashing detergent compositions, in particular automaticdishwashing compositions. It also relates to a process of preparingthese compositions. In particular the present invention relates to suchcompositions comprising particular types of non-ionic surfactants andwhich demonstrate good anti-spotting/shine properties on articlescleansed therewith.

BACKGROUND OF THE INVENTION

It is well known to use detergent compositions in the cleansing of hardsurfaces such as cleaning falls and walls and in dishwashing such asautomatic dishwashing.

However it is well known that washing hard surfaces with detergentcompositions can lead to the cleansed items suffering from spotting dueto mineral deposits being left behind once the cleansing operation hasbeen completed. These mineral deposits can be seen as spots on the itemsand also reduce the shine of the item which has been treated. Indishwashing operations, as well as other cleaning operations theappearance of a shiny surface is tremendously important to consumers asit is perceived as showing thorough and hygienic cleaning results.

The shine of a hard surface is determined mainly by the builder, thepolymer and the surfactant system used in the detergent used to cleanthe surface in question. Typically such detergent compositions areformulated to contain a builder. Builder such as the phosphate builderscan bind calcium and magnesium ions, act as alkalinity source for thedetergent and are used to buffer the wash liquor in a dishwasher at pH 9and above sometimes together with other chemicals such as disilicate,metasilicates and soda. Phosphates are also able to disperse existingcalcium carbonate in the wash liquor to prevent spotting on glasses asfor the aforementioned reasons this is seen as undesirable by theconsumer. Thus, phosphates in a detergent have at least four differentfunctions in an alkaline detergent; (1) Providing alkalinity; (2)buffering capacity, (3) complexing of magnesium and calcium ions; and(4) dispersing capacity of calcium carbonate. However, often the use ofbuilders alone is not sufficient to prevent the appearance of spottingon hard surfaces.

Accordingly there is a need in the art to provide detergent compositionsfor hard surfaces such as kitchenware, walls and floors, which show goodanti-spotting properties and which retain the shine on the surface ofthe item being cleansed. This is especially important for items such asglassware cleaned in a dishwashing operation such as in an automaticdishwashing machine.

It is an object of the present invention to address one or more of theabove-mentioned problems.

In particular, it is an object of the present invention to providedetergent compositions for hard surfaces, and in particular and(automatic) dishwashing detergent compositions which provide effectiveshine/anti-spotting properties on the surfaces it is used to cleanse.

STATEMENT OF INVENTION

It has surprisingly been found that one or more of the above problemsare addressed by the compositions of the present invention.

Thus according to a first aspect of the present invention there isprovided a liquid hard surface detergent composition comprising a) aliquid mixed alkoxylate fatty alcohol non-ionic surfactant comprising agreater number of moles of the lower higher alkoxylate group than of thehigher alkoxylate group in the molecule and b) a builder.

Preferably the composition is an automatic dishwashing detergentcomposition.

It is preferred that the detergent composition is a gel.

Preferably the mixed alkoxylate fatty alcohol non-ionic surfactantcomprises at least two of EO, PO or BO groups and most preferably onlyEO and PO groups.

The mixed alkoxylate fatty alcohol non-ionic surfactant preferably has amole ratio of the lower alkoxylate group to the higher alkoxylate groupis at least 1.1:1, most preferably of at least 1.8:1, especially atleast 2:1. It is also preferred that the mixed alkoxylate fatty alcoholnon-ionic surfactant comprises between 3 to 5 moles of the higheralkoxylate group and between 6 to 10 moles of the higher lower group,preferably 4 or 5 moles of PO and 7 or 8 moles of EO and most preferably4 moles of PO and 8 moles of EO.

Preferably the mixed alkoxylate fatty alcohol non-ionic surfactant has12-18 carbon atoms.

The detergent preferably comprises 2 to 30% wt of the mixed alkoxylatefatty alcohol non-ionic surfactant.

It is preferred that the detergent composition further comprises abuilder, preferably one selected from the phosphate-containing builders,polycarboxylic acids and their salts and amino acid based builders andmost preferably from tripolyphosphates, citrates, MGDA and GLDA andsalts or derivatives and mixtures thereof.

The detergent composition of the invention preferably further comprisesa polymer, especially a sulphonated polymer and most especially asulphonated polymer comprising monomers of a carboxylic acid or a saltthereof and a sulphonated monomer, especially acrylic acid and/or2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS).

It is most preferred that the compositions of the present inventioncomprise additional non-ionic surfactant to the claimed mixed alkoxylatefatty alcohol non-ionic surfactant.

According to a second aspect of the present invention there is provideda method of preparing a detergent composition according to any one ofthe preceding claims, wherein the detergent composition is prepared at atemperature in the range of from 25-80° C., preferably at a temperaturein the range of from 25-60° C. such as 30-50° C.

According to a third aspect the present invention provides a unit dosedetergent composition comprising a liquid hard surface detergentcomposition according to the first aspect of the invention, whichcomposition is enveloped in a water soluble or water dispersiblepackage. The water soluble or water dispersible package preferably has aplurality of compartments. The water soluble or water dispersiblepackage comprises polymeric packaging material which is preferablyselected from polyvinyl alcohol, celluloses and cellulose derivatives,starches, gelatine, polyglycolides, gelatine and polylactides copolymersor a mixture or co-polymer thereof.

According to a fourth aspect of the invention there is provided a methodof reducing spotting on a hard surface by contacting a hard surface witha composition according to the first aspect of the invention or a unitdose composition according to the third aspect of the invention. It ispreferred that the method is carried out in an automatic dishwashingmachine.

Surprisingly, it has been found that the detergent compositionsaccording to the present invention exhibit good anti-spotting and shineproperties upon hard surfaces, especially in dishwashing applicationssuch as in automatic dishwashers.

Unless stated otherwise, all amounts herein are given as the percentageby weight of active ingredient based upon the weight of the totalcomposition.

The term ‘substantially free of’ as used herein means less than 0.5% wtof the material in question based on the total weight of that materialin the detergent composition.

By the term ‘water soluble or water dispersible packaging’ as usedherein is meant a package which at least partially dissolves in water ordisperses in water at 20° C. within 10 minutes to allow for egress ofthe contents of the package into the surrounding water.

By the term ‘higher alkoxylate’ it is meant the alkoxylate group havingthe greatest number of carbon atoms in that alkoxylate group. By theterm ‘lower alkoxylate’ it is meant the alkoxylate group having thelowest number of carbon atoms in that alkoxylate group. Thus for a mixedalkoxylate fatty alcohol comprising ethoxylate (EO) and propoxylate (PO)groups the EO is the lower alkoxylate and the PO is the higheralkoxylate. Thus the detergent compositions of the invention comprisemixed alkoxylate fatty alcohols comprising a greater number of EO groupsthan PO groups. The same applies to other mixed alkoxylates such asthose containing EO and butoxylate (BO) or even PO and BO groups.

By the term ‘liquid surfactant’ as used herein is meant a surfactantwhich is liquid at 21° C.

A ‘liquid composition’ as used herein refers coherent composition whichshows a tendency to flow as a coherent mass. It includes liquids, gelsand pastes. For the avoidance of doubt it does not include solid bodies,granules or powders.

DETAILED DESCRIPTION

The present invention will now be described in further detail.

a) Detergent Composition Format

The composition of the invention may be type of hard surface detergentcompositions such as a floor or wall cleaning composition. However it ispreferred that the composition of the invention is a dishwashingcomposition and in particular an automatic dishwashing composition.

The detergent compositions of the present invention are in liquid formas herein defined. According to a preferred aspect of the presentinvention the dishwashing composition is a gel.

Preferably the detergent compositions of the invention are alkaline,more preferably having a pH in the range of 9-12 as a 1% wt solution at20° C., most preferably 9.5-11.5. However in some applications it ispossible to use less alkaline detergents e.g. those with a pH in therange of from 6.5 to 9, especially from 7 to 8.5 as a 1% wt solution at20° C.

The detergent compositions of the present invention may be made by anysuitable method as well known to the person skilled in the art. However,it is preferred that when the detergent composition is according to thesecond aspect of the invention.

b) Liquid Mixed Alkoxylate Fatty Alcohol Nonionic Surfactant

Non-ionic surfactants are preferred for automatic dishwashing and someother hard surface cleaning operations as they are considered to be lowfoaming surfactants.

The standard non-ionic surfactant structure is based on a fatty alcoholwith a carbon C₈ to C₂₀ chain, wherein the fatty alcohol has beenethoxylated or propoxylated. The degree of ethoxylation is described bythe number of ethylene oxide units (EO), and the degree of propoxylationis described by the number of propylene oxide units (PO). Surfactantsmay also comprise butylene oxide units (BO) as a result of butoxylationof the fatty alcohol. Preferably, this will be a mix with PO and EOunits. The surfactant chain can be terminated with a butyl (Bu) moiety.

The length of the fatty alcohol and the degree ofethoxylation/propoxylation determines if the surfactant structure has amelting point below room temperature or in other words if is a liquid ora solid at room temperature. It is believed that the mixed alkoxylatefatty alcohol non-ionic surfactant of the present invention providetheir advantages for spotting inhibition and shine at least partlybecause they are liquid at room temperature.

It is preferred that the mixed alkoxylate fatty alcohol nonionicsurfactant have a fast wetting properties on glass, plastic and metalsurfaces such that at least 90% of the surface is wetted in less than 30seconds.

The compositions of the invention comprise a liquid mixed alkoxylatefatty alcohol non-ionic surfactant comprising a greater number of molesof the lower higher alkoxylate group than of the higher alkoxylate groupin the molecule.

It is especially preferred that the mixed alkoxylate fatty alcoholnonionic surfactant comprises at least two of EO, PO or BO groups andespecially a mixture of EO and PO groups, preferably EO and PO groupsonly.

It is most preferred that the mole ratio of the lower alkoxylate groupto the higher alkoxylate group is at least 1.1:1, more preferably atleast 1.5:1, and most preferably at least 1.8:1, such as at least 2:1 oreven at least 3:1.

An especially preferred mixed alkoxylate fatty alcohol nonionicsurfactant according to the present invention comprises between 3 to 5moles of the higher alkoxylate group and between 6 to 10 moles thehigher lower group. Especially preferred are mixed alkoxylate fattyalcohol nonionic surfactants having 4 or 5 moles of the higheralkoxylate group and 7 or 8 moles of the lower alkoxylate group.According to one aspect of the invention a mixed alkoxylate fattyalcohol nonionic surfactant having 4 or 5 PO moles and 7 or 8 EO molesis especially preferred and good results have been obtained with forsurfactants with 4 PO moles and 8 EO moles. In an especially preferredembodiment the mixed alkoxylate fatty alcohol non-ionic surfactant isC12-15 8EO/4PO.

Surfactants of the above type which are ethoxylated monohydroxy alkanolsor alkylphenols which additionally comprisepoly-oxyethylene-polyoxypropylene block copolymer units may be used. Thealcohol or alkylphenol portion of such surfactants constitutes more than30%, preferably more than 50%, more preferably more than 70% by weightof the overall molecular weight of the non-ionic surfactant.

The mixed alkoxylate fatty alcohol non-ionic surfactants used in thecompositions of the invention may be prepared by the reaction ofsuitable monohydroxy alkanols or alkylphenols with 6 to 20 carbon atoms.Preferably the surfactants have at least 8 moles, particularly preferredat least 10 moles of alkylene oxide per mole of alcohol or alkylphenol.

Particularly preferred liquid mixed alkoxylate fatty alcohol non-ionicsurfactants are those from a linear chain fatty alcohol with 12-18carbon atoms, preferably 12 to 15 carbon atoms and at least 10 moles,particularly preferred at least 12 moles of alkylene oxide per mole ofalcohol.

When PO units are used they preferably constitute up to 25% by weight,preferably up to 20% by weight and still more preferably up to 15% byweight of the overall molecular weight of the non-ionic surfactant.

Suitable liquid mixed alkoxylate fatty alcohol non-ionic surfactants canbe found in the class of reverse block copolymers of polyoxyethylene andpoly-oxypropylene and block copolymers of polyoxyethylene andpolyoxypropylene initiated with trimethylolpropane.

Suitable types can also be described by the formula:R₁O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)[CH₂CH(OH)R₂]where R1 represents a linear or branched chain aliphatic hydrocarbongroup with 4-18 carbon atoms or mixtures thereof, R2 represents a linearor branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms ormixtures thereof, x is a value between 0.5 and 1.5 and y is a value ofat least 15.

Another group of suitable liquid mixed alkoxylate fatty alcoholnon-ionic surfactants can be found in the end-capped polyoxyalkylatednon-ionics of formula:R₁O[CH₂CH(R₃)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR₂where R₁ and R₂ represent linear or branched chain, saturated orunsaturated, aliphatic or aromatic hydrocarbon groups with 1-30 carbonatoms, R₃ represents a hydrogen atom or a methyl, ethyl, n-propyl,iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x is a valuebetween 1 and 30 and, k and j are values between 1 and 12, preferablybetween 1 and 5 with the proviso that the molecule contains more of thelower alkoxylate than of the higher alkoxylate. When the value of xis >2 each R₃ in the formula above can be different. R₁ and R₂ arepreferably linear or branched chain, saturated or unsaturated, aliphaticor aromatic hydrocarbon groups with 6-22 carbon atoms, where group with8 to 18 carbon atoms are particularly preferred. For the group R₃=H,methyl or ethyl are particularly preferred. Particularly preferredvalues for x are comprised between 1 and 20, preferably between 6 and15.

As described above, in case x>2, each R₃ in the formula can bedifferent. For instance, when x=3, the group R₃ could be chosen to buildethylene oxide (R₃═H) or propylene oxide (R₃=methyl) units which can beused in every single order for instance (PO)(EO)(EO), (EO)(PO)(EO),(EO)(EO)(PO), (PO)(EO)(PO) and (PO)(PO)(EO). Only the mixed alkoxylateshaving comprising more of the lower alkoxylate than of the higheralkoxylate are suitable as the claimed mixed alkoxylate fatty alcoholnonionic surfactant. The value 3 for x is only an example and biggervalues can be chosen whereby a higher number of variations of (EO) or(PO) units would arise.

Particularly preferred end-capped polyoxyalkylated alcohols of the aboveformula are those where k=1 and j=1 originating molecules of simplifiedformula:R₁O[CH₂CH(R₃)O]_(x)CH₂CH(OH)CH₂OR₂

Other suitable surfactants are disclosed in WO 95/01416, to the contentsof which express reference is hereby made.

In a particularly preferred embodiment of the present invention themixed alkoxylate fatty alcohol non-ionic surfactants have the generalformula;R₁-[EO]_(n)-[PO]_(m)-[BO]_(p)-Bu_(q)wherein:R₁ is an alkyl group of between C₈ and C₂₀;EO is ethylene oxide;PO is propylene oxide;BO is butylene oxide;Bu is butylenen and m are integers from 1 to 15;p is an integer from 0 to 15; andq is 0 or 1.

Examples of especially preferred mixed alkoxylate fatty alcoholnon-ionic surfactants can be found in the Plurafac™, Lutensol™ andPluronic™ ranges from BASF and the Genapol™ series from Clariant.

The claimed mixed alkoxylate fatty alcohol non-ionic surfactants, andespecially the C12-15 fatty alcohol 8EO, 4PO surfactant (commerciallyavailable as Genapol EP 2584 ex Clariant, Germany) exhibit;

-   -   Excellent wetting of plastic, glass, ceramic and stainless steel    -   Excellent temperature stability up to 90° C. for processing    -   Good compatibility with thickeners typically used in the liquid        detergent compositions (e.g. PEG)    -   Stability in alkaline conditions.

The use of a mixture of any of the aforementioned non-ionic surfactantsis suitable in compositions of the present invention, e.g. mixtures ofalkoxylated alcohols and hydroxy group containing alkoxylated alcohols,provided that they are liquid and have a greater number of moles of thelower higher alkoxylate group than of the higher alkoxylate group in themolecule.

It is preferred that the liquid detergent compositions of the inventioncomprise 2-30% wt of the liquid mixed alkoxylate fatty alcohol nonionicsurfactant more preferably 3-25% wt such as 5-20% wt. If the compositionof the invention are present as part of a multi-phase unit dosecomposition then preferably the claimed non-ionic surfactants arepresent an amount of from 0.1% wt to 15% wt, more preferably 0.5% wt to10% wt, such as 0.5 to 7.5% wt based on the total unit dose composition.

Without wishing to be bound by theory it is believed that the film ofthe surfactant molecules covering the surface of the tableware and thedishwasher prevents the deposition of calcium carbonate on the surfacesand so aids the reduction in spotting and improves the shine of thesurfaces being treated. A second and unexpected beneficial effect is anincreased “carry over” of surfactant from the main washing cycle intothe rinse cycle in the automatic dishwashing machine due to the highconcentration of surfactant. This is important for multi-benefitdetergents, because they are used without adding extra rinse aid intothe reservoir provided in the dishwasher.

Many technological processes require control of liquid spreading oversolid surfaces. When a drop is placed on a surface, it can completelywet, partially wet, or not wet the surface. Wetting can be defined interms of the contact angle ° of a liquid droplet on a particularsurface, with a smaller contact angle signifying greater wetting; acontact angle of between 0° and 90° is defined as highly wettable, with0° being defined as totally wettable.

By reducing the surface tension with the claimed surfactants non-wettingmaterial for water can be made to become partially or completelywetting. Surfactants are absorbed onto the liquid-vapor, solid-liquid,and solid-vapor interfaces, which modify the wetting behavior ofhydrophobic materials to reduce the free energy. When surfactants areabsorbed onto a hydrophobic surface, the polar head groups face into thesolution with the tail pointing outward. In more hydrophobic surfaces,surfactants may form a bilayer on the solid, causing it to become morehydrophilic. As the surfactants are absorbed, the solid-vapor surfacetension increases and the edges of the drop become hydrophilic. As aresult, the drop spreads and the appearance of spotting is reduced.

This process is time dependent, and the dynamic drop radius can becharacterized as the drop begins to spread. The contact angle changesare based on the following equation:cos θ(t)=cos θ₀+(cos θ_(∞)−cos θ₀)(1−e ^(−t/τ))

-   -   Θ₀ is the initial contact angle    -   Θ_(∞) is the final contact angle    -   τ is the surfactant transfer time scale

The wetting properties of a surfactant are therefore key to itsperformance in detergent compositions used on hard surfaces, such asdishwashing compositions as they regulating the amount of spots left onsurfaces as a result of drying of unevenly spread water droplets.

c) Builders

The compositions of the invention comprise a builder. A builder may alsobe included in any additional detergent composition used in amulti-phase unit dose composition with the composition of the invention.The detergent compositions May comprise conventional amounts ofdetergent builders which may be either phosphorous based ornon-phosphorous based, or a combination of both types. Suitable buildersare well known in the art.

If phosphorous containing builders are to be used then it is preferredthat mono-phosphates, di-phosphates, tripolyphosphates, polyphosphonatesor oligomeric-poylphosphates are used. The alkali metal salts of theseagents are preferred, in particular the sodium salts. An especiallypreferred phosphorous containing builder is sodium tripolyphosphate(STPP). Conventional amounts of the phosphorous-containing builders maybe used in the solid detergent compositions, typically in the range offrom 15% wt to 80% wt, such as 20% wt to 75% wt, more preferably 25% wtto 60% wt.

The non-phosphorous containing builder may be organic molecules withcarboxylic group(s), amino acid based compounds, a succinate basedcompound or a mixture thereof. The term ‘succinate based compound’ and‘succinic acid based compound’ are used interchangeably herein and thesecompounds are further described below.

Builder compounds which are organic molecules selected fromwater-soluble monomeric polycarboxylic acids and/or their acid forms maybe used according to the invention. Suitable polycarboxylic acidsinclude acyclic, alicyclic, heterocyclic and aromatic carboxylic acids.Suitable examples of such compounds include citric acid, fumaric acid,tartaric acid, maleic acid, lactic acid, (ethylenedioxy)diacetic acid,tartronic acid, lactic acid, glycolic acid, malonic acid, diglycolicacid and fumaric acid and salts and derivatives thereof, especially thewater soluble salts thereof. Preferred salts of the abovementionedcompounds are the ammonium and/or alkali or alkaline earth metal salts,e.g. the ammonium, lithium, sodium, potassium or calcium salts, andparticularly preferred salts are the sodium salts. These acids may beused in their monomeric or oligomeric form. An especially preferredbuilder is sodium citrate.

Preferred examples of amino acid based compounds according to theinvention are MGDA (methyl-glycine-diacetic acid, and salts andderivatives thereof) and GLDA (glutamic-N,N-diacetic acid) and salts andderivatives thereof. Other suitable builders are described in U.S. Pat.No. 6,426,229 which is incorporated by reference herein. A preferredMGDA compound is a salt of methyl glycine diacetic acid. Suitable saltsinclude the triammonium salt, the tripotassium salt and, preferably, thetrisodium salt. A preferred GLDA compound is a salt of glutamic diaceticacid. Suitable salts include the tetraammonium salt, the tetrapotassiumsalt and, preferably, the tetrasodium salt. Especially preferred are thesodium salts thereof.

In particular suitable builders include; for example, asparticacid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA),iminodisuccinic acid (IDA), aspartic acid-N-monopropionic acid (ASMP),N-(2-sulfomethyl) aspartic acid (SMAS), N-(2-sulfoethyl)aspartic acid(SEAS), N-(2-sulfomethyl)glutamic acid (SMGL), N-(2-sulfoethyl)glutamicacid (SEGL), N-methyliminodiacetic acid (MIDA), α-alanine-N,N-diaceticacid (α-ALDA), β-alanine-N,N-diacetic acid (β-ALDA), serine-N,N-diaceticacid (SEDA), isoserine-N,N-diacetic acid (ISDA),phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diaceticacid (ANDA), sulphanilic acid-N,N-diacetic acid (SLDA),taurine-N,N-diacetic acid (TUDA) and sulphomethyl-N,N-diacetic acid(SMDA) and alkali metal salts or ammonium salts thereof.

Preferred succinate compounds are described in U.S. Pat. No. 5,977,053and have the formula;

in which R, R¹, independently of one another, denote H or OH, R², R³,R⁴, R⁵, independently of one another, denote a cation, hydrogen, alkalimetal ions and ammonium ions, ammonium ions having the general formulaR⁶R⁷R⁸R⁹N+ and R⁶, R⁷, R⁸, R⁹, independently of one another, denotinghydrogen, alkyl radicals having 1 to 12 C atoms or hydroxyl-substitutedalkyl radicals having 2 to 3 C atoms. Iminodisuccinic acid (IDS) and(hydroxy)iminodisuccinic acid (HIDS) and alkali metal salts or ammoniumsalts thereof are especially preferred succinate based builder salts.Especially preferred are the sodium salts thereof.

MGDA, GLDA, IDS and HIDS are especially preferred amino acid based andsuccinate based builders according to the present invention and mixturesthereof may also be used.

Any suitable form of the amino acid and succinate based compounds in thepreceding paragraphs may be used.

Conventional amounts of these phosphorous free builders may be used,typically with an amount in the range of from 20% wt to 80% wt, such as25 or 30% wt to 60 or 70% wt being used.

According to one aspect of the present invention a mixture of aphosphorous containing builder such as STPP and a non-phosphorouscontaining builder such as MGDA, GLDA, IDS, HIDS and/or citrates may beused. The weight proportions of each builder can be selected accordingto the needs of the formulator.

Preferably the total amount of builder present in the composition is atleast 10 wt %, and most preferably at least 15 wt %, preferably in anamount of up to 80 wt %, preferably up to 65 wt %, more preferably up to60 wt %. The actual amount used in the compositions will depend upon thenature of the builder used.

d) Optional Ingredients

The detergent compositions of the invention may also comprise additionaloptional ingredients in addition to the claimed surfactant. Theseingredients may also be present in any other detergent composition usedin conjunction with the composition of the invention to form amulti-phase unit dose detergent composition. Where reference is madebelow to a weight percentage based it is to the weight percentage of thecomposition comprising that ingredient. For the composition of theinvention this is based simply upon the weight of that composition.Where the composition forms part of a multi-phase unit dose detergentcomposition the amount is stated as based upon the weight of that partof the multi-phase unit dose composition which contains the specifiedingredient.

In addition to the particular liquid mixed alkoxylated fatty alcoholsurfactants described above which are an essential component of thedetergent compositions of the invention, they may also comprise one ormore further surfactants. Any other detergent compositions used with thecompositions of the invention in the multi-phase unit dose compositionsof the invention may also comprise surfactant as described herein.

If any further surfactant is present it may be any of nonionic, anionic,cationic, amphoteric or zwitterionic surface active agents or mixturesthereof although cationic surfactants are less preferred. Many suchsuitable surfactants are described in Kirk Othmer's Encyclopedia ofChemical Technology, 3rd Ed., Vol. 22, pp. 360-379, “Surfactants andDetersive Systems”, incorporated by reference herein.

For automatic dishwashing compositions according to the presentinvention non-ionic surfactants are especially preferred. For othercleaning applications, such as floors and walls, other surfactants suchas anionic surfactants may also be included and suitable types are wellknown in the art.

The additional nonionic surfactants which may be used include any solidnonionic surfactant and any nonionic surfactants which do not containmore of the lower alkoxylate than of the higher alkoxylate.

Additional nonionic surfactants which may be used (excluding any fallinginto the essential liquid mixed alkoxylate fatty alcohol non-ionicsurfactants class above) include ethoxylated non-ionic surfactantsprepared by the reaction of a monohydroxy alkanol or alkylphenol with 6to 20 carbon atoms which are not liquid or which do not contain more ofthe lower alkoxylate than of the higher alkoxylate.

Preferably the surfactants have at least 12 moles particularly preferredat least 16 moles, and still more preferred at least 20 moles, such asat least 25 moles of ethylene oxide per mole of alcohol or alkylphenol.Particularly preferred non-ionic surfactants suitable for use as theadditional nonionic surfactants are those from a linear chain fattyalcohol with 16-20 carbon atoms and at least 12 moles, particularlypreferred at least 16 and still more preferred at least 20 moles, ofethylene oxide per mole of alcohol.

The additional fatty alcohol non-ionic surfactants may be prepared asdescribed above for the mixed alkoxylate fatty alcohol nonionicsurfactants.

The use of mixtures of different nonionic surfactants is suitable in thecontext of the present invention for instance mixtures of alkoxylatedalcohols and hydroxy group containing alkoxylated alcohols.

Preferably the total amount of non-ionic surfactants is in an amount offrom 0.1% wt to 20% wt, more preferably 0.5% wt to 15% wt, such as 1 to10% wt based on the weight of the composition(s) comprising thesurfactant.

An especially preferred optional ingredient in the detergentcompositions of the invention is a polymer. Suitable polymers includethose comprising polycarboxylic groups such as polyacrylate homopolymersand copolymers and the salts thereof. Copolymers of polycarboxylic acidssuch as acrylic acids with sulphonated monomers are especially preferredaccording to the present invention as it has been found that thecombination of a sulphonated polymer with the claimed surfactant systemprovides significant benefits in shine and anti-spotting properties ofthe detergent composition.

Preferred examples of the sulphonated polymers include copolymers ofCH₂═CR¹—CR²R³—O—C₄H₃R⁴—SO₃X wherein R¹, R², R³, R⁴ are independently 1to 6 carbon alkyl or hydrogen, and X is hydrogen or alkali with anysuitable other monomer units including modified acrylic, fumaric,maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonicacid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethylether, styrene and any mixtures thereof. Other suitable sulfonatedmonomers for incorporation in sulfonated (co)polymers are2-acrylamido-2-methyl-1-propanesulphonic acid,2-methacrylamido-2-methyl-1-propanesulphonic acid,3-methacrylamido-2-hydroxy-propanesulphonic acid, allysulphonic acid,methallysulphonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulphonicacid, 2-methyl-2-propenen-1-sulphonic acid, styrenesulphonic acid,vinylsulphonic acid, 3-sulphopropyl acrylate,3-sulphopropylmethacrylate, sulphomethylacrylamide,sulphomethylmethacrylamide and water soluble salts thereof. Suitablesulphonated polymers are also described in U.S. Pat. No. 5,308,532 andin WO 2005/090541.

It is especially preferred that the sulphonated polymer comprisesmonomers of a carboxylic acid and a sulphonated monomer, especiallyacrylic acid and/or 2-acrylamido-2-methyl-1-propanesulphonic acid(AMPS). It is most preferred that the sulphonated polymer is a copolymerof acrylic acid and AMPS, especially in a weight ratio (of the monomers)of 50:50 to 90:10, such as 70:30 to 80:20.

When a sulfonated polymer is present, it is preferably present in thedetergent composition of the invention in an amount of at least 0.5 wt%, preferably at least 1 wt %, more preferably at least 2 wt %, and mostpreferably at least 3 wt %, up to 40 wt %, preferably up to 30 wt %,more preferably up to 20 wt %, and most preferably up to 15 wt %.

In one embodiment of the invention for a multi-phase unit dosecomposition it is preferred that a sulphonated polymer is present in thedetergent composition of the invention and in at least one furtherdetergent composition forming at least one further phase of themulti-phase unit dose composition.

It is also possible to include a polymer which is a polyaspartic acidderivative of formula (I):

wherein:M is selected from the group H, alkali metals, ammonium, optionallysubstituted alkylammonium or a mixture thereof;X is selected from the group NR¹, O and S or a mixture thereof, whereinR¹ is H or C₁₋₂₀ hydrocarbyl optionally substituted with hydroxy or C₁₋₈alkyl;Z is R²Y_(n), wherein:R² is selected from the group comprising: linear or branched C₁-C₂₀alkyl, C₅₋₂₀ aralkyl, each optionally substituted with C₁₋₈ alkyl orcyclic C₃₋₁₀ alkyl, wherein the aralkyl may contain one or moreheteroatoms selected from N, O and S; and

-   -   linear and branched —R³—(R³O)_(p) or —R⁵—(N(R⁴)R⁵)_(q) wherein        R³ and R⁵ are selected from linear or branched C₁-C₁₀ alkyl and        wherein R⁴ is selected from the same group as R¹ and p and q are        integers from 1 to 100;        each Y is independently selected from the group of hydrophilic        substituents containing OH; OR¹⁰; SO₃M; SO₂M; SO₃R¹¹; SO₂R¹²;        OSO₃M; OSO₂M; OSO₃R¹¹; OSO₂R¹²; PO₃M; PO₂M, PO₃R¹¹; PO₂R¹²;        OPO₃M; OPO₂M, OPO₃R¹¹; OPO₂R¹²; COOM; COOR¹³ wherein R¹⁰, R¹¹,        R¹² and R¹³ are each selected independently from each other from        the group defined for R⁶; and/or the group of hydrophobic        substituents containing NR¹⁴R¹⁵ and NR¹⁴R¹⁵R¹⁶ wherein R¹⁴, R¹⁵        and R¹⁶ are each independently selected from linear or branched        C₁-C₂₀ alkyl, cyclic C₃₋₁₀ alkyl or C₅₋₂₀ aralkyl, each        optionally substituted with C₁₋₈ alkyl or cyclic C₃₋₁₀ alkyl,        wherein the aralkyl may contain one or more heteroatoms selected        from N, O and S;        R⁸ is H or is selected from the same group as R²;        provided that when X is NR¹, then Y is not SO₃M, SO₂M, SO₃R¹¹,        SO₂R¹², OSO₃M, OSO₂M, OSO₃R¹¹ or OSO₂R¹²;        n is an integer from 1 to 20;        k, l are each independently integers from 0 to 860; and        m is an integer from 1 to 860.

According to a further embodiment of the first aspect of the presentinvention, there is provided a composition comprising a compound offormula (I) as hereinbefore described wherein:

M is selected from the group H, alkali metals, ammonium, optionallysubstituted alkylammonium or a mixture thereof;

X is selected from the group NR¹, O and S or a mixture thereof, whereinR¹ is H or C₁₋₂₀ hydrocarbyl optionally substituted with hydroxy or C₁₋₈alkyl;

Z is R²Y_(n), wherein

R² is selected from the group comprising: linear or branched C₁-C₂₀alkyl, C₅₋₂₀ aralkyl, each optionally substituted with C₁₋₈ alkyl orcyclic C₃₋₁₀ alkyl, wherein the aralkyl may contain one or moreheteroatoms selected from N, O and S; and

linear and branched —R³—(R³O)_(p) or —R⁵—(N(R⁴)R⁵)_(q) wherein R³ and R⁵are selected from linear or branched C₁-C₁₀ alkyl and wherein R⁴ isselected from the same group as R¹ and p and q are integers from 1 to100;

each Y is independently selected from the group of hydrophilicsubstituents containing OH; OR¹⁰; SO₃M; SO₂M; SO₃ R¹¹; SO₂R¹²; OSO₃M;OSO₂M; OSO₃R¹¹; OSO₂R¹²; PO₃M; PO₂M, PO₃R¹¹; PO₂R¹²; OPO₃M; OPO₂M,OPO₃R¹¹; OPO₂R¹²; COOM; COOR¹³ wherein R¹⁰, R¹¹, R¹² and R¹³ are eachselected independently from each other from the group defined for R⁶;and/or the group of hydrophobic substituents containing H, NR¹⁴R¹⁵ andNR¹⁴R¹⁵R¹⁶ wherein R¹⁴, R¹⁵ and R¹⁶ are each independently selected fromlinear or branched C₁-C₂₀ alkyl, cyclic C₃₋₁₀ alkyl or C₅₋₂₀ aralkyl,each optionally substituted with C₁₋₈ alkyl or cyclic C₃₋₁₀ alkyl,wherein the aralkyl may contain one or more heteroatoms selected from N,O and S;R₈ is H or is selected from the same group as R²;provided that the molar ratio of hydrophobic:hydrophilic substituents isfrom 1:1.1 to 1:1000.n is an integer from 1 to 20;k, l are each independently integers from 0 to 860; andm is an integer from 1 to 860.

The polyaspartic acid derivatives may be included in the compositions ofthe invention in amounts 0.1-40% wt, such as 5-30% wt.

The compositions of the invention may also comprise one or morethickeners to control the viscosity thereof. Any suitable thickeners asknown in the art may be used with gums, polymers and gels beingpreferred. For example, polyethylene glycols, e.g. PEG with a molecularweight in the range of 5000 to 15,000 may be used as a thickener.Thickeners are typically present in amounts of up to 2% wt.

The detergent composition of the invention may also comprise one or morefoam control agents and indeed this is preferred. Suitable foam controlagents for this purpose are all those conventionally used in this field,such as, for example, silicones and their derivatives and paraffin oil.The foam control agents are preferably present in the composition inamounts of 0.5% by weight or less of the total weight of thecomposition.

The detergent compositions of the invention may also comprise minor,conventional, amounts of preservatives, dyes, colurants and perfume asdesired. Such ingredients are typically present in amounts of up to 2%wt.

Solvents may also be included in the liquid detergent compositions ofthe invention, for example glycols such as 1,2 propylene glycol.Typically solvents, if used are present in amounts of up to 10% wt,preferably in amounts of up to 5% wt.

The detergent compositions of invention may comprise bleaching compoundsalthough generally they will be substantially free of bleachingcompounds. The detergent composition of the invention may also be usedas part of a multi-phase unit dose detergent composition. In this casethe other detergent compositions making up the multi-phase unit dosedetergent composition may comprise a bleaching compound and preferablythey do so.

Any conventional bleaching compound can be used in any conventionalamount in either the composition of the invention or in any otherdetergent composition forming part of the multi-phase unit dosedetergent composition.

When a bleach is present, it is preferably present in the relevantcomposition in an amount of at least 1 wt %, more preferably at least 2wt %, more preferably at least 4 wt %. Preferably it is present in therelevant composition in an amount of up to 30 wt %, more preferably upto 20 wt %, and most preferably up to 15 wt %. Amounts of 1% to 30% wtof bleach component are especially preferred.

Most preferably the bleach is selected from inorganic peroxy-compoundsand organic peracids and the salts derived therefrom.

Examples of inorganic perhydrates include persulfates such asperoxymonopersulfate (KMPS), perborates or percarbonates. The inorganicperhydrates are normally alkali metal salts, such as lithium, sodium orpotassium salts, in particular sodium salts. The inorganic perhydratesmay be present in the detergent as crystalline solids without furtherprotection. For certain perhydrates, it is however advantageous to usethem as granular compositions provided with a coating which gives thegranular products a longer shelf life.

The preferred percarbonate is sodium percarbonate of the formula2Na₂CO₃.3H₂O₂. A percarbonate, when present, is preferably used in acoated form to increase its stability.

Organic peracids include all organic peracids traditionally used asbleaches, including, for example, perbenzoic acid and peroxycarboxylicacids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinicacid, diperoxydodecanedicarboxylic acid, diperoxy-azelaic acid andimidoperoxycarboxylic acid and, optionally, the salts thereof.Especially preferred is phthalimidoperhexanoic acid (PAP).

When a composition of the invention, or a unit dose compositioncomprising a composition of the invention, comprises a bleach it mayalso comprise one or more bleach activators or bleach catalystsdepending upon the nature of the bleaching compound. Any suitable bleachactivator may be included for example TAED. Any suitable bleach catalystmay be used for example manganese acetate or dinuclear manganesecomplexes such as those described in EP-A-1,741,774. Conventionalamounts may be used e.g. in amounts of from 1 to 30 t %, more preferredof from 5 to 25 wt % and most preferred of from 10 to 20 wt % based onthe weight of the part of the composition comprising the bleach.

The detergent compositions of the invention, or other detergentcompositions included in the multi-phase unit dose compositions, maycomprise one or more anti-corrosion agents especially when the detergentcompositions are for use in automatic dishwashing operations. Theseanti-corrosion agents may provide benefits against corrosion of glassand/or metal and the term encompasses agents that are intended toprevent or reduce the tarnishing of non-ferrous metals, in particular ofsilver and copper. It may be desirable to include more than one type ofanti-corrosion agent to provide protection against corrosion of glassand metals.

Organophosphoric acids are often used as corrosion inhibitors.Diphosphoric acids and their salts are preferred according to thepresent invention with the tetrasodium and disodium salts beingespecially preferred. 1, hydroxy, ethylidene 1,1-diphosphoric acid(HEDP) and it tetrasodium or disodium salts is especially preferred. Theorganophosphoric acid is preferably used in an amount of from 0.05 to10% wt, such as 0.1 to 7.5% wt based on the weight of the composition inwhich it is present.

It is known to include a source of multivalent ions in detergentcompositions, and in particular in automatic dishwashing compositions,for anti-corrosion benefits. For example, multivalent ions andespecially zinc, bismuth and/or manganese ions have been included fortheir ability to inhibit such corrosion. Organic and inorganicredox-active substances which are known as suitable for use assilver/copper corrosion inhibitors are mentioned in WO 94/26860 and WO94/26859. Suitable inorganic redox-active substances are, for example,metal salts and/or metal complexes chosen from the group consisting ofzinc, bismuth, manganese, titanium, zirconium, hafnium, vanadium, cobaltand cerium salts and/or complexes, the metals being in one of theoxidation states II, III, IV, V or VI. Particularly suitable metal saltsand/or metal complexes are chosen from the group consisting of MnSO₄,Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II)[1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆,K₂ZrF₆, CoSO₄, Co(NO₃)₂ and Ce(NO₃)₃. Any suitable source of multivalentions may be used, with the source preferably being chosen fromsulphates, carbonates, acetates, gluconates and metal-protein compounds.Zinc salts are specially preferred corrosion inhibitors.

Preferred silver/copper anti-corrosion agents are benzotriazole (BTA) orbis-benzotriazole and substituted derivatives thereof. Other suitableagents are organic and/or inorganic redox-active substances and paraffinoil. Benzotriazole derivatives are those compounds in which theavailable substitution sites on the aromatic ring are partially orcompletely substituted. Suitable substituents are linear or branch-chainC₁₋₂₀ alkyl groups and hydroxyl, thio, phenyl or halogen such asfluorine, chlorine, bromine and iodine. A preferred substitutedbenzotriazole is tolyltriazole (TTA).

Therefore, an especially preferred optional ingredient according to thepresent invention is a source of multivalent ions such as thosementioned in the immediately preceding paragraphs and in particularcompounds comprising zinc, bismuth and/or manganese ions and/orbenzotriazole, including substituted benzotriazoles. In particular asource of zinc ions and unsubstituted benzotriazole are preferred asanti-corrosion agents and a mixture of these two ingredients isespecially preferred according to the invention.

Any conventional amount of the anti-corrosion agents may be included inthe solid detergent compositions of the invention. However, it ispreferred that they are present in an total amount of from 0.01% wt to5% wt, preferably 0.05% wt to 3% wt; more preferably 0.1 to 2.5% wt,such as 0.2% wt to 2% wt based on the total weight of the composition.If more than one anti-corrosion agent is used, the individual amountsmay be within the preceding amounts given but the preferred totalamounts still apply.

The compositions of the invention may optionally comprise one or moreenzymes. Any type of enzyme typically used in detergent compositions maybe included in the compositions of the present invention. It ispreferred that the enzyme(s) is/are selected from proteases, lipases,amylases, cellulases laccases, catalases and peroxidases. It is mostpreferred that protease and/or amylase enzymes are included in thecompositions according to the invention as such enzymes are especiallyeffective in dishwashing detergent compositions. Any suitable species ofthese enzymes may be used as desired. Conventional amounts of suchenzymes may be used.

The compositions according to the invention, and/or any detergentcomposition used therewith in a multi-phase unit dose composition, mayalso comprise a source of acidity or a source of alkalinity (to obtainthe desired pH on dissolution) especially if the composition is to beused in an automatic dishwashing application.

A source of alkalinity may suitably be any suitable basic compound forexample any salt of a strong base and a weak acid. When an alkalinecomposition is desired silicates are amongst the suitable sources ofalkalinity. Preferred silicates are sodium silicates such as sodiumdisilicate, sodium metasilicate and crystalline phyllosilicates. Othersuitable sources of alkalinity may be a carbonate or bicarbonate (suchas the alkali metal or alkaline earth metal salts with sodium carbonatebeing especially preferred). A source of acidity may suitably be anysuitable acidic compound for example a polycarboxylic acid. Conventionalamounts of the alkalinity or acidity source may be used.

The detergent compositions can be prepared by any suitable method.However, it has been found that they exhibit especially good stabilityif they are produced by mixing the ingredients together at a temperaturein the range of from 25-50° C., preferably of from 30-40° C. This hasbeen found to result in liquid compositions which typically show goodstability for at least three months at room temperature.

The present invention also provides a method of improving shine and/orinhibiting spotting on hard surfaces such as kitchenware and especiallyglassware. In particular the method is carried out by treatingkitchenware items in an automatic dishwasher by the step of contacting adetergent composition according to either the first or second aspect ofthe invention with kitchenware items during a dishwashing cycle.Suitable conditions to effect the removal are employed in the method andwill typically involve contact under aqueous conditions and usually at atemperature in the range of from 15-70° C., such as 30-70° C.

According to third aspect of the invention it is preferred that thedetergent composition of the invention forms a part of an overalldishwashing composition such as a multi-phase unit dose composition. Aunit dose detergent composition is designed to be used as a singleportion of detergent composition in a single washing operation. Ofcourse, one or more of such single portions may be used in a cleaningoperation if desired. The additional detergent may be of any physicalform e.g. liquid, powder, granules, shaped body etc.

One type of preferred unit dose composition according to the presentinvention comprises the detergent composition of the invention at leastpartially enveloped by a water soluble or water dispersible package.Thus this is a unit dose detergent composition intended to be consumedin a single washing operation. It is preferred that the water soluble orwater dispersible packaging material fully envelopes the detergentcomposition. In this aspect the detergent composition of the inventionmay be present within the water soluble or dispersible package either onits own (e.g. as a gel encased in a water soluble single compartmentpackage) or it may form a part of a water soluble package containing twoor more different detergent compositions. In this latter arrangement itis preferred that the water soluble package is a multi-compartmentpackage with each compartment containing one or more detergentcompositions.

It is preferred according to one embodiment of the invention that thewater soluble or water dispersible package comprises a plurality ofcompartments, typically 2 to 5 compartments. This has the advantage ofallowing incompatible ingredients of the overall formulation to bephysically separated from each other which can increase the stability ofthe overall composition.

The water soluble or water dispersible package comprising the detergentof the invention may be of any suitable form e.g. flexible pouch or aself-supporting body such as one with a substantially planar base andupstanding side walls which container is typically closed with a filmlid. In some embodiments of the invention it may comprise a partiallypre-formed container. Preferred examples of such containers includegelatin capsules, such as those employed in medicament applications.When gelatin is used it will be appreciated that the formulation and thephysical nature of the gelatin may wary widely. For example the gelatinmay be a hard gelatin or a soft gelatin (having a plasticiser componentsuch as water, glycerine, mono-propylene glycol or polyethylene glycol).

As stated above the water soluble or water dispersible package may be inthe form of a self supporting body. Preferably this is a self-supportingbody with a substantially planar base and upstanding side walls which istypically closed with a film lid. Such a body may be of any shape butwill typically be of a substantially square or rectangular crosssection. The package may also not be in the form of a walled containerbut instead a shape, which is substantially self supporting (optionallywith pores/apertures). The self supporting body preferably comprises amatrix. The matrix may be formed of the material used for the film ofthe package or alternatively the matrix may comprise a second material.Preferred matrix forming materials include gelatin, especially in anadmixture with glycerine, optionally with water. A further preferredmatrix forming material is polyethylene glycol (PEG) having a molecularmass of 3000 or above, e.g. such as 6000, 8000, 20000, 35000 or 8million.

Generally the package has a maximum dimension in at least one plane ofbetween 5 and 60 mm, preferably between 10 and 50 mm, such as between 20and 45 mm. It will be appreciated that the size of the package will varyin accordance with desires of the unit dose detergent product formulatorand the intended use of the package. It is especially preferred that thepackage has this dimension in at least two planes and most preferably inthree planes.

The package may be formed by any suitable method, for example the methoddescribed in WO 2004/081161 which method is incorporated by referenceherein. If the package is a self supporting body produced by injectionmoulding then it can be made according to the process disclosed inEP-A-1232100 which is incorporated by reference herein.

When the package comprising the detergent composition is a flexiblepouch, the method may comprise the step of enveloping the detergentcomposition with at least one sheet of the material used to form thepackaging, especially a flexible sheet of the packaging material.

One way of producing the water soluble or water dispersible package inthe form of a pouch containing the detergent composition of theinvention is to form a cavity in a first sheet of the packaging materialused to form the pouch and add the detergent composition thereto priorto the packaging material being sealed to produce the water soluble orwater dispersible packaging pouch. The package may be sealed by theaddition of a second sheet of the packaging material over the cavitycontaining the detergent composition and sealing it to the first sheetof the packaging material. The first and second sheets of the packagingmaterial may comprise the same or different water soluble or dispersiblepackaging material however the two sheets preferably comprise the samepackaging material.

The water soluble or water dispersible package may be formed by anysuitable conventional method, for example, vacuum forming, thermoformingor injection moulding depending upon the type of packaging to beproduced e.g. flexible pouch or self supporting container. For example,in a thermoforming process the film may be drawn down or blown down intoa mould. Thus, for example, the film is heated to the thermoformingtemperature using a thermoforming heater plate assembly, and then drawndown under vacuum or blown down under pressure into the mould.

Plug-assisted thermoforming and pre-stretching the film, for example byblowing the film away from the mould before thermoforming, may, ifdesired, be used. One skilled in the art can choose an appropriatetemperature, pressure or vacuum and dwell time to achieve an appropriatepackage. The amount of vacuum or pressure and the thermoformingtemperature used depend on the thickness and porosity of the film and onthe polymer or mixture of polymers being used. Thermoforming of PVOHfilms is known and described in, for example, WO 00/55045.

Polyvinyl alcohol is one suitable material from which to form the waterdispersible or water soluble package (see further details below). Asuitable forming temperature for PVOH or ethoxylated PVOH is, forexample, from 90 to 130° C., especially 90 to 120° C. A suitable formingpressure is, for example, 69 to 138 kPa (10 to 20 p.s.i.), especially 83to 117 kPa (12 to 17 p.s.i.). A suitable forming vacuum is 0 to 4 kPa (0to 40 mbar), especially 0 to 2 kPa (0 to 20 mbar). A suitable dwell timeis, for example, 0.4 to 2.5 seconds, especially 2 to 2.5 seconds.

The packaging material used to produce the water soluble or waterdispersible package is preferably polymeric and is preferably selectedfrom polyvinyl alcohol, celluloses (including cellulose derivatives),starches, gelatine, polyglycolides, gelatine and polylactides copolymersor a mixture or co-polymer thereof. Polyvinyl alcohol is especiallypreferred as the packaging material. Preferred cellulose derivativesinclude hydroxypropyl cellulose ether (HMPC). The polymeric material maybe a photopolymer or a co-polymer of any suitable monomers such as thoseof the aforementioned types.

The water soluble or water dispersible polymeric material may, forexample, be formed of a film. The film may be a single film, or alaminated film as disclosed in GB-A-2,244,258. While a single film mayhave pinholes, the two or more layers in a laminate are unlikely to havepinholes which coincide.

The thickness of at least one, and preferably all, of the external wallsof the water soluble or water dispersible package may be up to 2 mm,more preferably up to 1 mm, more preferably 10 to 300 μm, morepreferably 20 to 200 μm, especially 25 to 160 μm, more especially 30 to150 μm and most especially 30 to 150 μm.

The packaging material, e.g. film, may be produced by any process, forexample by extrusion and blowing or by casting. The film may beunoriented, monoaxially oriented or biaxially oriented. If the layers inthe film are oriented, they usually have the same orientation, althoughtheir planes of orientation may be different if desired. The layers in alaminate may be the same or different. Thus they may each comprise thesame polymer or a different polymer.

Examples of the water-soluble or dispersible polymeric material whichmay be used in a single layer film or in one or more layers of alaminate or which may be used for injection moulding or blow mouldingare poly(vinyl alcohol) (PVOH), cellulose derivatives such ashydroxypropyl methyl cellulose (HPMC) and gelatin. An example of asuitable PVOH is ethoxylated PVOH. The PVOH may be partially or fullyalcoholised or hydrolysed. For example it may be from 40 to 100%,preferably from 70 to 92%, more preferably about 88% or about 92%,alcoholised or hydrolysed. The degree of hydrolysis is known toinfluence the temperature at which the PVOH starts to dissolve in water.88% hydrolysis corresponds to a film soluble in cold (i.e. roomtemperature) water, whereas 92% hydrolysis corresponds to a film solublein warm water. Therefore the water soluble characteristics of the filmcan be controlled.

The invention is further described with reference to the followingnon-limiting Examples. Further examples within the scope of theinvention will be apparent to the person skilled in the art.

EXAMPLES Example 1

Two multi-phase unit dose automatic dishwashing compositions having theformulations as shown below in Table 1 were prepared as described below.The compositions comprise a gel according to the invention and also twoadditional powder compositions herein designated as powder 1 and powder2. The gel composition and the two powder compositions are placed intoseparate compartments of a water soluble injection moulded pre-formedpolyvinylalcohol container having three compartments to form themulti-phase unit dose composition. All percentages are given as % wtbased on the total weight of the composition.

Formulation 1 is a comparative example comprising gel detergentcomposition an ethoxylated fatty alcohol non-ionic surfactant which isnot according to the present invention comprises a gel detergentcomposition according to the invention. Formulation 2 comprises a geldetergent composition according to the invention.

Powder 1 is formed by mixing together the given amounts of sodiumcarbonate, sodium percarbonate and sodium tripolyphosphate.

Powder 2 is formed by mixing together the given amounts of TAED,Protease granules, Amylase granules, Manganese acetate and thesulfonated copolymer.

The gel composition is formed by mixing the liquid non-ionic surfactant,the two thickeners (PEG 6000 and the EO/PO thickener) with the sodiumtripolyphosphate (for use in gel) in an Ystral X50/10 mixer at roomtemperature for 20 minutes at a speed or 1000 revolutions per minuteuntil it yielded a fine dispersion of solids and liquids which formed agel. This dispersion did not show any appreciable phase separation afterthree months storage at room temperature.

TABLE 1 Formulation 1 Formulation 1 Component in wt % (comparative)Formulation 2 Powder 1 Sodium carbonate 8.0 8.0 Sodium percarbonate 15.015.0 Sodium Tripolyphosphate (STPP) 45.0 45.0 Powder 2 TAED 5.0 5.0Protease granules 1.0 1.0 Amylase granules 0.5 0.5 Managanese acetate0.5 0.5 Sulfonated co-polymer*¹ 8.0 8.0 Gel composition of the inventionLiquid nonionic surfactant 5.0 0.0 (C₁₁-EO₅-PO₅), Liquid nonionicsurfactant 0.0 5.0 (C₁₂-C₁₅-EO₈-PO₄), Sodium Tripolyphosphate (STPP)10.0 10.0 for gel PEG 6000 as thickener 1.5 1.5 Statistical EO-POthickener 0.5 0.5 with mole ratio 4:1 and Mw 12000 g/mol. Total % wt100.0 100.0 pH measured 1 wt % in water at 9.8 9.8 20° C. *¹Available exRohm and Haas, a copolymer of Acrylic acid and AMPS in a wt ratio of74:26.

For both formulations, 8.5 g of Powder 1 was placed into a firstcompartment of the polyvinyl alcohol water soluble capsule. 4.5 g ofPowder 2 was placed into a second compartment of the polyvinyl alcoholwater soluble capsule. 3.0 g of the gel composition of the invention wasplaced into a third compartment of the polyvinyl alcohol water solublecapsule. The water soluble filled capsule was then sealed with aPolyvinyl alcohol water soluble film (Monosol PT 75). The capsule weightwas 2.5 g. Thus the total filled capsule weight was 18.5 g.

Example 2

Formulation 1 and Formulation 2 were tested for their shineprofile/anti-spotting properties in a Bosch SGS058M02EU/36 dishwashingmachine using the Eco 50° C.+Vario Speed (no 3-in-1 function) programfollowing the Rinse Performance method as described below.

A capsule according to Formulation 1 or Formulation 2 was added into thedosing chamber of the dishwasher and the machine was run on the abovedishwashing program. The dishwasher was loaded with glassware (longdrink glasses) as described below. The water hardness was 21° GH. Thistest is repeated 5 times for each formulation.

Spotting/filming on the long drink glassware after 5 dishwashing cycleswas assessed by viewing the glasses in a lit black box. The results aregiven in Table 2 and are expressed on a scale of 1 to 10 (1 being worstwith extreme spotting and filming and 10 being best with no visiblespotting and filming).

TABLE 2 Rinse Performance Formulation 1 (comparative) Formulation 2Spotting 3.0 6.0 Filming 7.0 7.0

The rinse performance results above demonstrate that the compositions ofthe invention exhibit better anti-spotting properties that thecomparative example. This also results in a better perception of shineon the glasses by the consumer.

The invention claimed is:
 1. A method of automatic dishwashing, whereinthe method comprises the steps of: carrying out at least one mainwashing cycle and at least one rinse cycle in an automatic dishwashingmachine; and providing a composition to the automatic dishwashingmachine during the at least one main washing cycle; wherein thecomposition is a liquid automatic dishwashing detergent compositioncomprising: a liquid mixed alkoxylate fatty alcohol non-ionic surfactantcomprising at least one lower alkoxylate group and at least one higheralkoxylate group, wherein there is a greater number of moles of thelower alkoxylate group than of the higher alkoxylate group in themolecule, wherein the liquid mixed alkoxylate fatty alcohol non-ionicsurfactant has the formula:R1-[EO]n-[PO]m-[BO]p-Buq wherein: R1 is an alkyl group of between C8 andC20; EO is ethylene oxide; PO is propylene oxide; BO is butylene oxide;Bu is butylene; n is an integer from 6 to 10; m is an integer from 3 to5; p is 0; q is 0; and a builder.
 2. The method according to claim 1,wherein the liquid automatic dishwashing detergent composition is a gel.3. The method according to claim 1, wherein the liquid mixed alkoxylatefatty alcohol non-ionic surfactant comprises 4 moles of PO and 8 molesof EO in the molecule.
 4. The method according to claim 1, wherein theliquid automatic dishwashing detergent composition comprises 2 to 30% wtof the liquid mixed alkoxylate fatty alcohol non-ionic surfactant. 5.The method according to claim 1, wherein the builder is selected fromphosphate-containing builders, polycarboxylic acids and their salts andamino acid based builders.
 6. The method according to claim 5, whereinthe builder is selected from tripolyphosphates, citrates, MGDA and GLDAand salts or derivatives and mixtures thereof.
 7. The method accordingto claim 1, wherein the liquid automatic dishwashing detergentcomposition further comprises a polymer.
 8. The method according toclaim 7, wherein the polymer is a sulphonated polymer.
 9. The methodaccording to claim 8, wherein the sulphonated polymer comprises monomersof a carboxylic acid or a salt thereof and a sulphonated monomer. 10.The method according to claim 1, wherein the liquid automaticdishwashing detergent composition further comprises additional non-ionicsurfactant.
 11. The method according to claim 1, wherein the liquidautomatic dishwashing detergent composition is prepared at a temperaturein the range of from 25-80° C.
 12. The method according to claim 11,wherein the liquid automatic dishwashing detergent composition isprepared at a temperature in the range of from 30-50° C.
 13. The methodaccording to claim 1, wherein the liquid automatic dishwashing detergentcomposition is in the form of a unit dose and is enveloped in a watersoluble or water dispersible package.
 14. The method according to claim13, wherein the water soluble or water dispersible package has aplurality of compartments.
 15. The method according to claim 13, whereinthe water soluble or water dispersible package comprises polymericpackaging material.
 16. The method according to claim 15, wherein thepolymeric packaging material is selected from polyvinyl alcohol,celluloses and cellulose derivatives, starches, gelatine,polyglycolides, gelatine and polylactides copolymers or a mixture orco-polymer thereof.
 17. The method according to claim 1, wherein theliquid mixed alkoxylate fatty alcohol non-ionic surfactant is derivedfrom a linear chain fatty alcohol having 12-15 carbon atoms.
 18. Themethod according to claim 1, wherein the liquid mixed alkoxylate fattyalcohol non-ionic surfactant has at least 10 moles of alkylene oxide permole of alcohol.
 19. The method according to claim 1, wherein the liquidautomatic dishwashing detergent composition comprises at least 2 wt % ofthe liquid mixed alkoxylate fatty alcohol non-ionic surfactant.
 20. Themethod according to claim 1, wherein the liquid automatic dishwashingdetergent composition comprises at least 10 wt % of the builder.
 21. Themethod according to claim 1, wherein any solvent included in the liquidautomatic dishwashing detergent composition is present in an amount ofno more than 10 wt %.
 22. The method according to claim 1, wherein theliquid mixed alkoxylate fatty alcohol non-ionic surfactant comprises 4or 5 moles of PO and 7 or 8 moles of EO.
 23. The method according toclaim 1, wherein the liquid mixed alkoxylate fatty alcohol non-ionicsurfactant is derived from a linear chain fatty alcohol having 12-18carbon atoms.